EP0003449B1 - Procédé de fabrication par coextrusion d'un matériau composite polyfluorure de vinylidène et polyuréthane - Google Patents
Procédé de fabrication par coextrusion d'un matériau composite polyfluorure de vinylidène et polyuréthane Download PDFInfo
- Publication number
- EP0003449B1 EP0003449B1 EP79400018A EP79400018A EP0003449B1 EP 0003449 B1 EP0003449 B1 EP 0003449B1 EP 79400018 A EP79400018 A EP 79400018A EP 79400018 A EP79400018 A EP 79400018A EP 0003449 B1 EP0003449 B1 EP 0003449B1
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- EP
- European Patent Office
- Prior art keywords
- polyurethane
- pvf
- polyvinylidene fluoride
- die
- extruders
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
- B29C48/147—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle
- B29C48/1472—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle at the die nozzle exit zone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
- B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
- B29C48/335—Multiple annular extrusion nozzles in coaxial arrangement, e.g. for making multi-layered tubular articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/007—Using fluid under pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/02—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
- B32B2309/14—Velocity, e.g. feed speeds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2375/00—Polyureas; Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]
Definitions
- the present invention relates to a process for the production of a polyvinylidene fluoride composite material, a polymer presented in the abbreviated form: PVF 2 , - polyurethane obtained by coextrusion and, by extension, coextrusion-blowing, the latter variant being assimilated to coextrusion and does not differentiating it only by injecting a gas inside the extruded object which is still hot in order to increase its volume, or give it a particular shape.
- thermoplastics The technique of coextrusion of at least two thermoplastics is well known, it is in particular described in POLYMER PLASTICS TECHNOLOGY AND ENGINEERING, Volume 3, pages 49 to 68: "Coextruded films - Process and Properties" by John E. GUILLOTTE.
- thermoplastics In general, three ways are known of coextruding thermoplastics from conventional extruders in a number equal to the number of polymers to be extruded.
- the first process consists in extruding the polymers separately and joining them together at the outlet of the dies.
- the second method consists in feeding a single die by means of at least two extruders, the die comprising as many channels as there are extruders, and consequently of polymers to be extruded. The polymer flows meet at the level of the lips of the die, therefore substantially just before its exit.
- the third method consists in supplying a flow distributor by means of the desired number of extruders. In this distributor, the polymers come together in a single flow which feeds the sector. In these methods, the respective flow rates of the extruders usually make it possible to adjust the relative thicknesses of the extruded polymers.
- PVF 2 While many polymers can be coextruded, PVF 2 could not be systematically combined with proper adhesion to other polymers using this technique. The reason probably stems from the lack of compatibility of PVF 2 with most other polymers and the well-known lack of adhesion of fluororesins with the majority of extrudable polymers.
- United States patent 3,801,429 at least 35 coextrudable associations of a polymer with PVF 2 .
- resins known to be compatible with PVF 2 make it possible to obtain a homogeneous composite material by coextrusion.
- this process for manufacturing PVF 2- polyurethane composite material is characterized in that the flows of PVF 2 and of polyurethane at the outlet of two extruders are brought together at the latest at the lips of a single die, the extruded PVF 2. being in a range of apparent viscosity at 200 ° C. such that it exhibits, at least for two speed gradients in the table below, apparent viscosities respectively included between the two extreme apparent viscosities indicated, and the extruded polyurethane having an apparent viscosity at 200 ° C at most four times less than that of PVF 2 for the speed gradients used to define the latter.
- PVF 2 is also understood to mean not only the homopolymer, but also copolymers containing at least 70% by weight of PVF 2 or mixtures of PVF 2 with other polymers.
- the essential condition is that these copolymers or blends have the viscosity characteristics previously mentioned.
- thermoplastic polyurethanes coextruded with PVF 2 are preferably linear or weakly crosslinked polyurethanes generally obtained by reaction of an organic diisocyanate with a polyether and / or polyester diol of molecular weight between 500 and 6000, the extension of the chains being caused by difunctional molecules such as low molecular weight diols, diacids, diamines, water, or mixtures thereof, in the presence or absence of a catalyst.
- polyether or polyester diols usually known for this kind of reaction with diisocyanates
- the equipment used to produce the PVF 2- polyurethane composite material consists of extruders, of the die and possibly of the conventional flow distributor commonly used in the technique of coextrusion of thermoplastic polymers.
- the adjustment of the flow rate of each of the extruders depends on the thickness of each of the polymer layers.
- the temperature of the die is between 180 ° C. and 230 ° C., the temperatures of the extruders being those usually expected in the case of simple extrusion of each of the polymers.
- PVF 2 and / or polyurethane As in the case of polymers usually coextrudable, it is possible to incorporate into PVF 2 and / or polyurethane conventional adjuvants such as fillers, pigments, plasticizers, stabilizers and others. It is also possible to incorporate various polymers or copolymers into the polyurethane, provided however that the mixture contains at least 50% by weight of polyurethane and retains an apparent viscosity identical to that which the polyurethane should preferably have as a function of PVF 2 ,
- PVF 2- polyurethane composite materials obtained according to the process described come in all the forms usually achievable by coextrusion of the polymers. They can be for example in the form of film, plate, tube, profile, sheath, container of any shape obtained by coextrusion-blowing.
- Two extruders (SAMAFOR B.30 type) are available with screw length 20 times the diameter and compression ratio 3.5 so that they feed a flow distributor cylinder itself fixed to an ordinary flat die. intended to make a plate 0.6 mm thick and 300 mm wide.
- a PVF 2 (FORAFLON 1000 HD from the company CHEMICALS UGINE KUHLMANN) is extruded with an apparent viscosity at 200 ° C. of 75.10 3 and 18.4.10 3 poises for speed gradients in sec-1 respectively of 11, 8 and 118.
- the heating temperatures displayed for this extruder are 180 ° C at the inlet, 200 ° C for the first body and 200 ° C for the second body.
- thermoplastic polyurethane (ESTANE 58271) with an apparent viscosity at 200 ° C. of 2, b is extruded. 10 3 and 1,2.10 3 poises for speed gradients in sec- 'of 11.8 and 118 respectively.
- the heating temperatures displayed for this extruder are from the input of: 150 ° C-160 ° C- 180 ° C.
- the die and the flow distributor are maintained at 200 ° C.
- the flow rates of the two machines are adjusted so that the film obtained has a thickness of approximately 150 microns for PVF 2 and 350 microns for polyurethane.
- the extruded film is received between the cylinders of a calender heated to 120 ° C.
- a PVF Z- polyurethane composite film is obtained, the two layers of which are inseparable.
- extruders identical to those of Example 1 are available. These extruders supply a flow distributor fixed to a die making it possible to manufacture a tube. A conventional "internal" type conformator, slightly conical and cooled by water circulation, is fixed to the die.
- the die and the flow distributor are maintained at 200-210 ° C.
- a PVF Z- polyurethane composite tube is obtained, consisting of two perfectly adherent layers, 0.5 mm thick each.
- Example 2 The procedure is as in Example 2, but a third extruder identical to the previous ones, supplied with polyethylene (LOTREN 3003), is added at the level of the flow distributor.
- the displayed heating temperatures are, starting from the entrance, 180 ° C-190 ° C-200 ° C.
- a composite tube which consists of three layers which are presented in the following order: PVF 2 ⁇ mixture based on polyurethane - polyethylene. These polymer layers adhere perfectly to each other.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Description
- La présente invention concerne un procédé de fabrication d'un matériau composite polyfluorure de vinylidène, polymère présenté sous la forme abrégée: PVF2, - polyuréthane obtenu par coextrusion et, par extension, coextrusion-soufflage cette dernière variante étant assimilée à la coextrusion et ne s'en différenciant que par l'injection d'un gaz à l'intérieur de l'objet extrudé encore chaud afin d'en augmenter son volume, ou, lui donner une forme particulière.
- La technique de coextrusion d'au moins deux thermoplastiques est bien connue, elle est en particulier décrite dans POLYMER PLASTICS TECHNOLOGY AND ENGINEERING, Volume 3, pages 49 à 68: "Coextruded films - Process and Properties" par John E. GUILLOTTE.
- De façon générale, on connaît trois façons de procéder à la coextrusion des thermoplastiques à partir d'extrudeuses conventionnelles en nombre égal au nombre de polymères à extruder. Le premier procédé consiste à extruder séparément les polymères et à les réunier en sortie de filières. Le deuxième procédé consiste à alimenter une filière unique au moyen d'au moins deux extrudeuses, la filière comportant autant de canaux qu'il y a d'extrudeuses, et par conséquent de polymères à extruder. Les flux de polymères se rejoignent au niveau des lèvres de la filière donc sensiblement juste avant la sortie de celle-ci. Le troisième procédé consiste à alimenter un répartiteur de flux au moyen du nombre voulu d'extrudeuses. Dans ce répartiteur les polymères se réunissent en un flux unique qui alimente la filière. Dans ces procédés les débits respectifs des extrudeuses permettent habituellement de régler les épaisseurs relatives des polymères extrudés.
- Alors que de nombreux polymères peuvent être coextrudés, le PVF2 n'a pu être associé de façon systématique avec une adhérence correcte, aux autres polymères au moyen de cette technique. La raison provient probablement du manque de compatibilité du PVF2 avec la plupart des autres polymères et du manque d'adhérence bien connu des résines fluorées avec la majorité des polymères extrudables. A titre d'exemples sont citées dans le brevet des Etats-Unis d'Amérique 3 801 429 au moins 35 associations coextrudables d'un polymère avec le PVF2. Or seules les 10 associations à base de résines acryliques ou méthacryliques, résines connues comme compatibles avec le PVF2, permettent d'obtenir par coextrusion un matériau composite homogène.
- Il est également connu d'extruder du PVF2 avec un polyuréthane d'après le brevet GB 1 238,215, mais il s'agit d'une coextrusion selon le 1 er procédé dans lequel il n'est pas nécessairement recherché une adhérence entre les 2 matériaux.
- Selon la présente invention, il est maintenant possible d'obtenir par coextrusion un matériau composite de PVFZ polyuréthane, les polymères adhérant l'un à l'autre sans avoir à utiliser un intermédiaire de collage, à condition de coextruder un PVF2 possédant une viscosité bien spécifique et un polyuréthane thermoplastique dont la viscosité est adaptée à du PVF2. Il est en effet constaté que si le PVF2 est trop fluide ou trop visqueux par rapport au yuréthane, l'interpénétration des polymères au cours de la coextrusion ne se faisant pas, il n'est pas possible d'obtenir un matériau composite dont les polymères adhèrent l'un à l'autre.
- En pratique ce procédé de fabrication de matériau composite PVF2-polyuréthane est caractérisé en ce que les flux de PVF2 et de polyuréthane en sortie de deux extrudeuses sont réunis au plus tard au niveau des lèvres d'une filière unique, le PVF2 extrudé se trouvant dans une gamme de viscosité apparente à 200°C telle qu'il présente au moins pour deux gradients de vitesse du tableau ci-après des viscosités apparentes respectivement incluses entre les deux viscosités apparentes extrêmes inidiquées,
- Les viscosités apparentes dont il est fait état précédemment sont mesurées de façon connue au moyen d'un rhéomètre capillaire, en tenant compte de la correction de RABINOWITCH appliquée aux liquides newtoniens.
- Pour les besoins de l'invention on entend également par PVF2, non seulement l'homopolymère, mais encore les copolymères contenant au moins 70% en poids de PVF2 ou les mélanges de PVF2 avec d'autres polymères, La condition essentielle est que ces copolymères ou mélanges possèdent les caractéristiques de viscosités précédemment citées.
- Les polyuréthanes thermoplastiques coextrudés avec le PVF2 sont de préférence des polyuréthanes linéaires ou faiblement réticulés obtenus de façon générale par réaction d'un diisocyanate organique avec un diol polyéther et/ou polyester de poids moléculaire compris entre 500 et 6000, l'allongement des chaines étant provoqué au moyen de molécules difonctionnelles telles que les diols de faible poids moléculaire, des diacides, des diamines, de l'eau, ou leurs mélanges, en présence ou non de catalyseur. Parmi la famille des diols polyéthers ou polyesters habituellement connus pour ce genre de réaction avec les diisocyanates, on peut également inclure les polyols polyethers ou polyesters copolymérisés ou greffés avec l'acrylonitrile, l'acrylonitrile-styrène, le méthylstyrène, le chlorure de vinyle, le chlorure de vinylidène ou le méthacrylate de méthyle.
- L'appareillage utilisé à le réalisation du matériau composite PVF2-polyuréthane est constitué d'extrudeuses, de filière et éventuellement de répartiteur de flux classiques et couramment employés dans la technique de coextrusion des polymères thermoplastiques. Comme déjà signalé, du réglage du débit de chacune des extrudeuses dépend l'épaisseur de chacune des couches de polymère. Pour les besoins de l'invention la température de la filière est comprise entre 180°C et 230°C, les températures des extrudeuses étant celles habituellement prevues dans le cas de la simple extrusion de chacun des polymères.
- Afin que l'adhérence finale entre la PVF2 et le polyuréthane soit bien assurée, il est recommandé de procéder à la coextrusion de ces deux polymères de façon telle que les flux de chacune des matières sortant des extrudeuses soient réunis au plus tard au niveau des lèvres de la filière. Il est même préférable que les flux de PVF2 et de polyuréthane en sortie d'extrudeuse cheminent ensemble et en contact sur une certaine longueur avant d'atteindre les lèvres de la filière. Das ce dernier cas à la place d'une filière à plusieurs canaux, on interpose un répartiteur de flux entre le sortie des extrudeuses et une filière à canal unique.
- Comme dans le cas de polymères habituellement coextrudables, il est possible d'incorporer au PVF2 et/ou polyuréthane les adjuvants classiques comme les charges, les pigments, les plastifiants, les stabilisants et autres. Il est également possible d'incorporer au polyuréthane divers polymères ou copolymères, à condition toutefois que le mélange contienne au moins 50% en poids de polyuréthane et conserve une viscosité apparente identique à celle que devrait avoir de préférence le polyuréthane en fonction du PVF2,
- Les matériaux composites PVF2-polyuréthane obtenus selon le procédé décrit se présentent sous toutes les formes réalisables habituellement par coextrusion des polymères. Ils peuvent être par exemple sous forme film, plaque, tube, profilé, gaine, récipient de forme quelconque obtenu par coextrusion-soufflage.
- Les exemples suivants illustrent l'objet de l'invention. Pour tous les exemples les mesures de viscosité ont été effectuées au moyen d'un rhéomètre capillaire INSTRON Model 3211 avec un capillaire d'environ 50,8 mm (2 in.) de longueur pour un diamètre de buse d'environ 1,27 mm (0,05 in).
- On dispose de deux extrudeuses (type SAMAFOR B.30) de longueur de vis de 20 fois le diamètre et de taux de compression 3,5 de telle sorte qu'elles alimentent un cylindre répartiteur de flux fixé lui- même à une filière plate ordinaire destinée à fabriquer une plaque de 0,6 mm d'épaisseur et de 300 mm de largeur.
- De la première machine on extrude un PVF2 (FORAFLON 1000 HD de la Société PRODUITS CHIMIQUES UGINE KUHLMANN) de viscosité apparente à 200°C de 75.103 et 18,4.103 poises pour des gradients de vitesse en sec-1 respectivement de 11,8 et 118. Les températures de chauffe affichées pour cette extrudeuse sont de 180°C en entrée, 200°C pour le premier corps et 200°C pour le deuxième corps.
- De la seconde machine on extrude un polyuréthane thermoplastique (ESTANE 58271) de viscosité apparente à 200°C de 2,b. 103 et 1,2.103 poises pour des gradients de vitesse en sec-' respectivement de 11,8 et 118. Les températures de chauffe affichées pour cette extrudeuse sont en partant de l'entrée de: 150°C-160°C-180°C.
- La filière et le répartiteur de flux sont maintenus à 200°C.
- Les débits des deux machines sont réglés de façon à ce que le film obtenu ait une épaisseur d'environ 150 microns pour le PVF2 et 350 microns pour le polyuréthane.
- Le film extrudé est reçu entre les cylindres d'une calandre chauffés à 120°C.
- On obtient un film composite PVFZ-polyuréthane dont les deux couches sont inséparables.
- On dispose de deux extrudeuses identiques à celles de l'exemple 1. Ces extrudeuses alimentent un répartiteur de flux fixé à une filière permettant de fabriquer un tube. Un conformateur classique de type "interne," légèrement conique et refroidi par circulation d'eau, est fixé à la filière.
- De la première machine on extrude dans les mêmes conditions le même PVF2 de l'exemple 1.
- De la seconde machine on extrude un mélange, obtenu par regranulation dans une boudineuse, de 35 parties en poids d'un copolymère à base de polyéthylène et d'acide acrylique et de 65 parties en poids du polyuréthane de l'exemple 1. Pour une viscosité apparente du PVF2 à 200°C de 141.103 et 8,8.103 poises pour des gradients de vitesse en sec-1 respectivement de 3,5 et 354, la viscosité apparente à 200°C du mélange à base de polyuréthane est respectivement pour ces mêmes gradients de vitesse en sec-1 de 9,2.103 et 1,9.103. Les températures de chauffe affichées pour cette extrudeuse sont, en partant de l'entrée, de 170°C-180°C-190°C.
- La filière et le répartiteur de flux sont maintenus à 200-210°C.
- On obtient un tube composite PVFZ-polyuréthane constitué de deux couches parfaitement adhérentes de 0,5 mm d'épaisseur chacune.
- On opère selon l'exemple 2 mais on adjoint au niveau du répartiteur de flux une troisième extrudeuse identique aux précédentes, alimentée de polyéthylène (LOTREN 3003). Les températures de chauffe affichées sont, en partant de l'entrée, de 180°C-190°C-200°C.
- On obtient un tube composite constitué de trois couches qui se présentent dans l'ordre suivant: PVF2―mélange à base de polyuréthane - polyéthylène. Ces couches de polymère adhèrent parfaitement entre elles.
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7801590 | 1978-01-20 | ||
FR7801590A FR2415000A1 (fr) | 1978-01-20 | 1978-01-20 | Materiau composite polyfluorure de vinylidene et polyurethane obtenu par coextrusion |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0003449A1 EP0003449A1 (fr) | 1979-08-08 |
EP0003449B1 true EP0003449B1 (fr) | 1982-06-16 |
Family
ID=9203679
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79400018A Expired EP0003449B1 (fr) | 1978-01-20 | 1979-01-09 | Procédé de fabrication par coextrusion d'un matériau composite polyfluorure de vinylidène et polyuréthane |
Country Status (6)
Country | Link |
---|---|
US (2) | US4221757A (fr) |
EP (1) | EP0003449B1 (fr) |
JP (1) | JPS54110285A (fr) |
DE (1) | DE2963088D1 (fr) |
FR (1) | FR2415000A1 (fr) |
IT (1) | IT1118284B (fr) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1119928B (it) * | 1978-09-25 | 1986-03-19 | Ugine Kuhlmann | Materiale composito di polifluoruro di vinilidene e di polimero termoplastico incompatibile e procedimento per la sua fabbricazione |
FR2465320A1 (fr) * | 1979-09-14 | 1981-03-20 | Thomson Csf | Film de materiau composite piezo-electrique et son procede de fabrication |
FR2477463A1 (fr) * | 1980-03-07 | 1981-09-11 | Ugine Kuhlmann | Procede de fabrication d'un composite polyfluorure de vinylidene et polymere non compatible par coextrusion-moulage |
JPS57142359A (en) * | 1981-02-28 | 1982-09-03 | Kureha Chemical Ind Co Ltd | Extruded laminate |
JPS58147355A (ja) * | 1982-02-25 | 1983-09-02 | 平岡織染株式会社 | 可撓性積層体 |
US4585701A (en) * | 1984-02-15 | 1986-04-29 | Pennwalt Corporation | Composites of polyvinylidene fluoride alloys and thermoplastic polymers and their preparation |
FR2577564B1 (fr) * | 1985-02-14 | 1987-07-17 | Atochem | Procede de traitement de surface du polyfluorure de vinylidene en vue de son adhesion a un substrat. materiau obtenu a partir du polyfluorure de vinylidene traite |
JPH069917B2 (ja) * | 1985-05-09 | 1994-02-09 | 株式会社八興 | 2層式合成樹脂チューブ |
US5284710A (en) * | 1991-09-17 | 1994-02-08 | Crane Plastics Company | Fluoropolymer-acrylic plastic composite and coextrusion method |
NO950845L (no) * | 1994-03-10 | 1995-09-11 | Atochem Elf Sa | Tråder, rep, kabler og stag, dekket med en krympbar polymer, samt en fremgangsmåte for fremstilling derav |
US5589028A (en) * | 1994-11-03 | 1996-12-31 | Elf Atochem North America, Inc. | Bonding method employing tie layers for adhering polyethylene to fluoropolymers |
US5700578A (en) * | 1995-06-26 | 1997-12-23 | Crane Plastics Company Limited Partnership | Fluoropolymer/terpolymer composite |
US5848769A (en) * | 1996-08-26 | 1998-12-15 | Minnesota Mining & Manufacturing Company | Drag reduction article |
US6444311B1 (en) | 1999-10-19 | 2002-09-03 | Saint-Gobain Performance Plastics Corporation | Impact resistant protective multilayer film |
US20050074605A1 (en) * | 2003-10-01 | 2005-04-07 | Agrawal Purushottam Das | Thermoplastic multi-layer laminates |
WO2006095857A1 (fr) * | 2005-03-10 | 2006-09-14 | Daikin Industries, Ltd. | Copolymere de chlorotrifluoroethylene contenant un stratifie et procedes de production associes |
US9662869B2 (en) * | 2007-02-08 | 2017-05-30 | Meissner Filtration Products, Inc. | Multilayer film, method of making the same and containers formed from the same |
US7866348B2 (en) * | 2008-05-01 | 2011-01-11 | Saint-Gobain Performance Plastics Corporation | Multi-layered fuel tubing |
US8092881B2 (en) | 2008-05-01 | 2012-01-10 | Saint-Gobain Performance Plastics Corporation | Multi-layered fuel tubing |
EP2283989B1 (fr) * | 2009-08-06 | 2012-11-28 | Mondi Belcoat, Naamloze Vennootschap | Procédé de fabrication de couches monolithiques très minces de polyuréthane thermoplastique |
JP5795269B2 (ja) * | 2012-01-05 | 2015-10-14 | Imsテクノ株式会社 | シートおよびその製造方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3111450A (en) * | 1961-02-01 | 1963-11-19 | Armstrong Cork Co | Polyvinyl fluoride film capable of being adhesively secured and method |
US3397428A (en) * | 1964-08-14 | 1968-08-20 | Dow Chemical Co | Apparatus for the preparation of thermoplastic resinous composite articles |
US3476627A (en) * | 1966-04-12 | 1969-11-04 | Du Pont | Process for coextruding multiple-layered thermoplastic sheeting |
US3558330A (en) * | 1967-09-21 | 1971-01-26 | Dow Chemical Co | Packaging film and package |
US3801429A (en) * | 1969-06-06 | 1974-04-02 | Dow Chemical Co | Multilayer plastic articles |
DE2114065C2 (de) * | 1971-03-23 | 1982-08-19 | Heinrich Pannenbecker | Verfahren zur Herstellung von Folien aus thermoplastischen Kunststoffen mit Klebereigenschaft |
US4051293A (en) * | 1971-03-29 | 1977-09-27 | Cosden Oil & Chemical Company | Co-extrusion of polyvinylidene fluoride/polystyrene multiple-layered sheeting |
US3968196A (en) * | 1971-03-29 | 1976-07-06 | Cosden Oil & Chemical Company | Method of co-extrusion of polyvinylidene fluoride/polystyrene multiple-layered sheeting |
US3805848A (en) * | 1971-12-22 | 1974-04-23 | Parker Hannifin Corp | Hose construction |
CA994026A (en) * | 1972-05-18 | 1976-07-27 | Pennwalt Corporation | Vinylidene fluoride polymer film-forming composition in aqueous dispersion |
US3900616A (en) * | 1972-10-20 | 1975-08-19 | Dow Chemical Co | Process for coating a nonporous substrate with a vinylidene chloride polymer using a thermoplastic polyurethane precoat |
US4021405A (en) * | 1975-03-20 | 1977-05-03 | American Cyanamid Company | Polymer substrates coated with stabilized polymeric coating composition |
FR2382488A1 (fr) * | 1977-03-04 | 1978-09-29 | Ugine Kuhlmann | Procede de traitement du polyfluorure de vinyle en vue de son adherence avec un autre polymere |
-
1978
- 1978-01-20 FR FR7801590A patent/FR2415000A1/fr active Granted
-
1979
- 1979-01-09 EP EP79400018A patent/EP0003449B1/fr not_active Expired
- 1979-01-09 DE DE7979400018T patent/DE2963088D1/de not_active Expired
- 1979-01-11 IT IT67053/79A patent/IT1118284B/it active
- 1979-01-15 US US06/003,633 patent/US4221757A/en not_active Expired - Lifetime
- 1979-01-18 JP JP345179A patent/JPS54110285A/ja active Granted
-
1980
- 1980-01-17 US US06/112,957 patent/US4291099A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US4291099A (en) | 1981-09-22 |
EP0003449A1 (fr) | 1979-08-08 |
JPS6250300B2 (fr) | 1987-10-23 |
DE2963088D1 (en) | 1982-08-05 |
IT7967053A0 (it) | 1979-01-11 |
US4221757A (en) | 1980-09-09 |
FR2415000B1 (fr) | 1981-10-02 |
FR2415000A1 (fr) | 1979-08-17 |
IT1118284B (it) | 1986-02-24 |
JPS54110285A (en) | 1979-08-29 |
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